Hybrid copolymers

ABSTRACT

Hybrid copolymers for use as anti-scalant and dispersant. The polymers are useful in compositions used in aqueous systems. The polymers include at least one synthetic monomeric constituent that is chain terminated by a naturally occurring hydroxyl containing moiety. A process for preparing these hybrid copolymers is also provided.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.60/701,380, filed 21 Jul. 2005.

BACKGROUND OF THE INVENTION

Field of the Invention. The present invention relates to hybridcopolymers of synthetic and naturally derived materials. Moreparticularly, the present invention is directed towards chain transferagents formed from hydroxyl-containing naturally derived materials foruse during production of synthetic polymers to produce those hybridcopolymers. The present invention also relates to anti-scalant and/ordispersant formulations or compositions including such polymers andtheir use in aqueous systems, including scale minimization.

Background Information. Many aqueous industrial systems require variousmaterials to remain in a soluble, suspended or dispersed state. Examplesof such aqueous systems include boiler water or steam generatingsystems, cooling water systems, gas scrubbing systems, pulp and papermill systems, desalination systems, fabric, dishware and hard surfacecleaning systems, as well as downhole systems encountered during theproduction of gas, oil, and geothermal wells. Often the water in thosesystems either naturally or by contamination contains ingredients suchas inorganic salts. These salts can cause accumulation, deposition, andfouling problems in aqueous systems such as those mentioned above.

Inorganic salts are typically formed by the reaction of metal cations(e.g., calcium, magnesium or barium) with inorganic anions (e.g.,phosphate, carbonate or sulfate). When formed, the salts tend to beinsoluble or have low solubility in water. As their concentration insolution increases or as the pH and/or temperature of the solutioncontaining those salts changes, the salts can precipitate from solution,crystallize and form hard deposits or scale on surfaces. Such scaleformation is a problem in equipment such as heat transfer devices,boilers, secondary oil recovery wells, and automatic dishwashers, aswell as on substrates washed with such hard waters, reducing theperformance and life of such equipment.

In addition to scale formation many cooling water systems made fromcarbon steel, including industrial cooling towers and heat exchangers,experience corrosion problems. Attempts to prevent this corrosion areoften made by adding various inhibitors such as orthophosphate and/orzinc compounds to the water. However, phosphate addition increases theformation of highly insoluble phosphate salts such as calcium phosphate.The addition of zinc compounds can lead to precipitation of insolublesalts such as zinc hydroxide and zinc phosphate.

Other inorganic particulates such as mud, silt and clay can also becommonly found in cooling water systems. These particulates tend tosettle onto surfaces, thereby restricting water flow and heat transferunless they are effectively dispersed.

Stabilization of aqueous systems containing scale-forming salts andinorganic particulates involves a variety of mechanisms. Inhibition isone conventional mechanism for eliminating the deleterious effect ofscale-forming salts. In inhibition, synthetic polymer(s) are added thatincrease the solubility of the scale-forming salt in the aqueous system.

Another stabilization mechanism is the dispersion of precipitated saltcrystals. Synthetic polymers having carboxylic acid groups function asgood dispersants for precipitated salts such as calcium carbonates. Inthis mechanism, the crystals stay dispersed rather than dissolving inthe aqueous solution.

A third stabilization mechanism involves interference and distortion ofthe crystal structure of the scale by the polymer, thereby making thescale less adherent to surfaces, other forming crystals and/or existingparticulates.

Synthetic polymers can also impart many useful functions in cleaningcompositions. For example, they can function either independently orconcurrently as viscosity reducers in processing powdered detergents.They can also serve as anti-redeposition agents, dispersants, scale anddeposit inhibitors, crystal modifiers, and/or detergent assistantscapable of partially or completely replacing materials used as builderswhile imparting optimum detergent action properties to surfactants.

Cleaning formulations contain builders such as phosphates and carbonatesfor boosting their cleaning performance. These builders can precipitateout insoluble salts such as calcium carbonate and calcium phosphate inthe form of calcium orthophosphate. The precipitants form deposits onclothes and dishware that results in unsightly films and spots on thesearticles. Similarly, insoluble salts cause major problem in down holeoil field applications. Hence, there is a need for polymers that willminimize the scaling of insoluble salts in water treatment, oil fieldand cleaning formulations.

Synthetic polymers have been used to minimize scale formation in aqueoustreatment systems for a number of years. However, there has been ashortage of monomers to produce these synthetic polymers lately due torising demand and tight crude oil supplies. Hence, there is a need toreplace these synthetic polymers with hybrid polymers that are at leastpartially derived from renewal natural sources. Also, polymers fromrenewal natural sources should have a better biodegradable profile thansynthetic polymers, which tend to have very little biodegradability.

A number of attempts have been made in the past to use natural materialsas polymeric building blocks. These have mainly centered on graftingnatural materials like sugars and starches with synthetic monomers. Forexample, U.S. Pat. Nos. 5,854,191, 5,223,171, 5,227,446 and 5,296,470disclose the use of graft copolymers in cleaning applications.

Graft copolymers are produced by selectively generating initiation sites(e.g., free radicals) for the growth of monomer side chains from thesaccharide or polysaccharide backbone (CONCISE ENCYCLOPEDIA OF POLYMERSCIENCE AND ENGINEERING, J. I. Kroschwitz, ed., Wiley-Interscience, NewYork, p. 436 (1990)). These grafting techniques typically use Fe(II)salts such as ferrous sulfate or Ce(IV) salts (e.g., cerium nitrate orcerium sulfate) to create those initiation sites on the saccharide orpolysaccharide backbone (see, e.g., U.S. Pat. No. 5,304,620). Such redoxprocesses are not easily controlled, are inefficient and generateunwanted homopolymers. Also, cerium salts tend to be left in theresulting solution as unwanted byproducts, thereby presenting apotential negative effect on performance. Therefore, there is a need fornatural materials as polymeric building blocks that do not provide thoseproblems associated with graft copolymers.

SUMMARY OF THE INVENTION

The present invention discloses hybrid copolymers compositions derivedfrom synthetic monomers chain terminated with a hydroxyl containingnatural material. By using a hydroxyl containing natural material as thechain transfer agent, the molecular weight of the resultant polymer canbe controlled, especially if the chain transfer agent is low inmolecular weight. Further, no special initiation system is required,unlike graft copolymers. As noted above, grraft copolymers typicallyrequire special redox initiating systems containing metallic ions. Incontrast, hybrid copolymers according to the present invention useconventional free radical initiating systems.

The materials are also structurally different than graft copolymersdisclosed in the art. Graft copolymers are defined as a backbone of onemonomer or polymer and one or more side chains derived from anothermonomer(s) attached on to the backbone (Odian, George, PRINCIPLES OFPOLYMERIZATION, 2^(nd) ed., Wiley-Interscience, New York, p. 424(1981)). Graft copolymers (such as those described in U.S. Pat. Nos.5,854,191, 5,223,171, 5,227,446 and 5,296,470) typically have a naturalpolymer backbone and short side chains derived from synthetic monomers.In contrast, the hybrid copolymers of the present invention have longchains of synthetic monomers that incorporate a moiety derived fromnatural material at the end of the chain. From Mark, Herman F.,ENCYCLOPEDIA OF POLYMER SCIENCE AND TECHNOLOGY, 3^(rd) ed., Vol. 11,Wiley-Interscience, New York, p. 380 (2004), fragments of a chaintransfer agent are incorporated into polymer chains as end groups. Atransfer reaction can therefore be used to introduce specific end groupsinto the polymeric material.

These hybrid copolymers are effective at minimizing a number ofdifferent scales, including phosphate, sulfonate, carbonate and silicatebased scales. These scale-minimizing polymers are useful in a variety ofsystems, including water treatment compositions, oil field relatedcompositions, cement compositions, cleaning formulations and otheraqueous treatment compositions. Polymers according to the presentinvention have been found to be particularly useful in minimizing scaleby inhibition of scale formation, dispersion of precipitants, andinterference and distortion of crystal structure.

It has now been found that hydroxyl containing naturally derivedmaterials can be used as chain transfer agents during the production ofsynthetic polymers, thereby producing novel hybrid polymeric materials.These hydroxyl containing naturally derived materials include glycerol,citric acid and gluconic acid, as well as monosaccharides,oligosaccharides and polysaccharides such as sugars, maltodextrins andstarches. The resulting materials have the performance properties ofsynthetic polymers but use lower cost, readily available andenvironmentally friendly materials derived from renewable sources. Thesematerials can be used in water treatment, detergent, oil field and otherdispersant applications.

When present in aqueous treatment compositions, the hybrid copolymer ispresent in an amount of about 0.001% to about 25% by weight of theaqueous treatment composition. In another aspect, the polymer is presentin an amount of about 0.5% to about 5% by weight of the composition.

In one aspect, the number average molecular weight of the hybridcopolymer is between about 1000 and about 100,000. In another aspect,the number average molecular weight of the polymer is between about 2000and about 25,000.

The hybrid copolymer is useful in cleaning formulations. In suchformulations the polymer is present in an amount of about 0.01% to about10% by weight of the cleaning formulation. These cleaning formulationscan include phosphorus-based and/or carbonate builders. The cleaningformulations include automatic dishwashing detergent formulations.Automatic dishwashing detergent formulation can also have ingredientssuch as builders, surfactants, enzymes, solvents, hydrotropes, fillers,bleach, perfumes and/or colorants.

The hybrid copolymer is also useful in water treatment systems forpreventing calcium carbonate and phosphate scales. In such systems, thepolymer is present in an amount of at least about 0.5 mg/L. The hybridcopolymer is also useful in water treatment compositions or formulationsfor preventing calcium scales in a water treatment system. In thosewater treatment compositions the polymer is present in an amount ofabout 10% to about 25% by weight of the composition.

The present invention further provides for a mineral dispersant havingthe hybrid copolymer. This dispersant is able to disperse a variety ofminerals such as talc, titanium dioxide, mica, precipitated calciumcarbonate, ground calcium carbonate, precipitated silica, silicate, ironoxide, clay, kaolin clay or combinations thereof.

In another aspect, the hybrid copolymer can be used in a treatmentcomposition for aqueous systems for minimizing carbonate and/or sulfatescale.

In another application, the hybrid copolymer can be used in an aqueoustreatment system such as a water treatment system, oilfield system orcleaning system. When the aqueous treatment system is an oilfieldsystem, the sulfate scale minimized can be barium sulfate scale.

In yet even another application, the hybrid copolymer can be used as abinder for fiberglass. Fiberglass insulation products are generallyformed by bonding glass fibers together with a polymeric binder.Typically, an aqueous polymer binder is sprayed onto matted glass fiberssoon after they have been formed and while they are still hot. Thepolymer binder tends to accumulate at the junctions where fibers crosseach other, thereby holding the fibers together at these points. Heatfrom the hot fibers vaporizes most of the water in the binder. Thefiberglass binder must be flexible so that the final fiberglass productcan be compressed for packaging and shipping and later recover to itsfull vertical dimension when installed.

Accordingly, the present invention provides a method of preparing ahybrid copolymer wherein a monomeric solution and a naturally derivedhydroxyl containing chain transfer agent are polymerized in the presenceof an initiator solution. The initiator solution is not a metal ionbased redox system. The monomeric solution is present in an amount offrom about 25% to about 99.9% by weight and the chain transfer agent ispresent in an amount of from about 0.1% by weight to about 75% byweight, based on total weight of the copolymer.

The present invention also provides a hybrid copolymer having asynthetic polymer as the backbone of the copolymer, and a naturallyderived hydroxyl containing polymer as the chain terminating portion ofthe copolymer.

The present invention is further directed towards a water treatmentcomposition for use in preventing carbonate and phosphate scales in awater treatment system comprising the above described hybrid copolymer,wherein the polymer is present in the composition in an amount of about10% to about 25% by weight of the composition.

The present invention is further directed towards a cleaning formulationcomprising the above described hybrid copolymer, wherein the polymer ispresent in an amount of about 0.01% to about 10% by weight of thecleaning formulation. The cleaning formulation can include one or morephosphorus-based and/or carbonate builders. The cleaning formulation caninclude one or more surfactants.

The cleaning formulations include automatic dishwashing detergentformulations. These automatic dishwashing detergent formulations canalso include builders, surfactants, enzymes, solvents, hydrotropes,fillers, bleach, perfumes and/or colorants.

The cleaning formulations also include powdered or liquid or unit dosedetergent formulations.

The above described hybrid copolymer can be used in mineral dispersants.Mineral dispersants include those that disperse minerals such as talc,titanium dioxide, mica, precipitated calcium carbonate, ground calciumcarbonate, precipitated silica, silicate, iron oxide, clay, kaolin clayor combinations thereof.

The above described hybrid copolymer can be used in aqueous systemtreatment composition, wherein the aqueous system treatment compositionis able to modify calcium carbonate crystal growth in an aqueous system.Examples of aqueous systems include water treatment systems, oilfieldsystems or cleaning systems. In another aspect, the aqueous systemtreatment composition is able to minimize sulfate scale. In a furtheraspect the aqueous system can be an oilfield system and the sulfatescale minimized is barium sulfate scale.

The above described hybrid copolymer can further be used in a binder forfiberglass. It can also be used in a superabsorbent or rheologymodifier.

DETAILED DESCRIPTION OF THE INVENTION

The hybrid copolymers according to the present invention are produced byusing hydroxyl-containing naturally derived materials as chain transferagents during the production process. These hydroxyl containingnaturally derived materials range from small molecules such as glycerol,citric acid, lactic acid, tartaric acid, gluconic acid, glucoheptonicacid, monosaccharides and disaccharides such as sugars, to largermolecules such as oligosaccharides and polysaccharides (e.g.,maltodextrins and starches). Examples of these include sucrose,fructose, maltose, glucose, and saccharose, as well as reaction productsof saccharides such as mannitol, sorbitol and so forth. The chaintransfer agents include oxidatively, hydrolytically or enzymaticallydegraded monosaccharides, oligosaccharides and polysaccharides, as wellas chemically modified monosaccharides, oligosaccharides andpolysaccharides. Such chemically modified derivatives includecarboxylates, sulfonates, phosphates, phosphonates, aldehydes, silanes,alkyl glycosides, alkyl-hydroxyalkyls, carboxy-alkyl ethers and otherderivatives.

Use of natural materials as a chain transfer agent is an attractive andreadily available substitute for current synthetic materials. Forexample, glycerol is a by-product of biodiesel production. Glycerol isalso a by-product of oils and fats used in the manufacture of soaps andfatty acids. It can also be produced by fermentation of sugar. Citricacid is produced industrially by fermentation of crude sugar solutions.Lactic acid is produced commercially by fermentation of whey,cornstarch, potatoes, molasses, etc. Tartaric acid is one byproduct ofthe wine making process.

Polysaccharides useful in the present invention can be derived fromplant, animal and microbial sources. Examples of such polysaccharidesinclude starch, cellulose, gums (e.g., gum arabic, guar and xanthan),alginates, pectin and gellan. Starches include those derived from maizeand conventional hybrids of maize, such as waxy maize and high amylose(greater than 40% amylose) maize, as well as other starches such aspotato, tapioca, wheat, rice, pea, sago, oat, barley, rye, and amaranth,including conventional hybrids or genetically engineered materials.

Also included are hemicellulose or plant cell wall polysaccharides suchas D-xylans. Examples of plant cell wall polysaccharides includearabino-xylans such as corn fiber gum, a component of corn fiber. Animportant feature of these polysaccharides is the abundance of hydroxylgroups. These hydroxyl groups provide sites for chain transfer duringthe polymerization process. The higher the number of secondary andtertiary hydroxyl groups in the molecule the more effective it will beas chain transfer agent.

Other polysaccharides useful as chain transfer agents includemaltodextrins, which are polymers having D-glucose units linkedprimarily by α-1,4 bonds and have a dextrose equivalent (‘DE’) of lessthan about 20. Maltodextrins are available as a white powder orconcentrated solution and are prepared by the partial hydrolysis ofstarch with acid and/or enzymes. In one aspect the chain transfer agentsare glycerol, citric acid, maltodextrins and/or low molecular weightoxidized starches. Useful chain transfer agents according to the presentinvention have molecular weights of less than about 20,000. In anotheraspect, the chain transfer agents have molecular weights of less thanabout 2000. In even another aspect, chain transfer agents according tothe present invention have molecular weights of less than 1000.

Polysaccharides can be modified or derivatized by etherification (e.g.,via treatment with propylene oxide, ethylene oxide,2,3-epoxypropyltrimethylammonium chloride), esterification (e.g., viareaction with acetic anhydride, octenyl succinic anhydride (‘OSA’)),acid hydrolysis, dextrinization, oxidation or enzyme treatment (e.g.,starch modified with α-amylase, β-amylase, pullanase, isoamylase orglucoamylase), or various combinations of these treatments.

The hydroxyl-containing naturally derived chain transfer agents can beused from about 0.1 to about 75 weight % based on total weight of thepolymer. In one aspect, the range is from about 1 to about 50 weight %of chain transfer agents based on total weight of the polymer.

In one embodiment, the hybrid copolymers are prepared from at least onehydrophilic acid monomer as the synthetic constituent. Examples of suchhydrophilic acid monomers include but are not limited to acrylic acid,methacrylic acid, ethacrylic acid, α-chloro-acrylic acid, α-cyanoacrylic acid, β-methyl-acrylic acid (crotonic acid), α-phenyl acrylicacid, β-acryloxy propionic acid, sorbic acid, α-chloro sorbic acid,angelic acid, cinnamic acid, p-chloro cinnamic acid, β-styryl acrylicacid (1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid,citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaricacid, tricarboxy ethylene, 2-acryloxypropionic acid,2-acrylamido-2-methyl propane sulfonic acid, vinyl sulfonic acid, sodiummethallyl sulfonate, sulfonated styrene, allyloxybenzene sulfonic acidand maleic acid. Moieties such as maleic anhydride or acrylamide thatcan be derivatized to an acid containing group can be used. Combinationsof acid-containing hydrophilic monomers can also be used. In one aspectthe acid-containing hydrophilic monomer is acrylic acid, maleic acid,methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid ormixtures thereof.

In addition to the hydrophilic monomers described above, hydrophobicmonomers can also be used as the synthetic constituent. Thesehydrophobic monomers include, for example, ethylenically unsaturatedmonomers with saturated or unsaturated alkyl, hydroxyalkyl, alkylalkoxygroups, arylalkoxy, alkarylalkoxy, aryl and aryl-alkyl groups, alkylsulfonate, aryl sulfonate, siloxane and combinations thereof. Examplesof hydrophobic monomers include styrene, a-methyl styrene, methylmethacrylate, methyl acrylate, 2-ethylhexyl acrylate, octyl acrylate,lauryl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexylmethacrylate, octyl methacrylate, lauryl methacrylate, stearylmethacrylate, behenyl methacrylate, 2-ethylhexyl acrylamide, octylacrylamide, lauryl acrylamide, stearyl acrylamide, behenyl acrylamide,propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate,1-vinyl naphthalene, 2-vinyl naphthalene, 3-methyl styrene, 4-propylstyrene, t-butyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene,2-ethyl-4-benzyl styrene, and 4-(phenyl butyl)styrene. Combinations ofhydrophobic monomers can also be used.

The polymerization process can be a solution or suspension process. Theprocess involves polymerization using free radical initiators with oneor more of the above hydrophilic and/or hydrophobic monomers, and thehydroxyl containing natural products used as chain transfer agents orchain stoppers. These chain transfer agents can be added either at thebeginning of the reaction or during reaction as the monomer(s) is (are)added.

One advantage of this system is that it makes use of typical freeradical initiators. Unlike grafting systems, special redox systems suchas Ce(IV) salts are not required. Instead, easy-to-use thermallyactivated initiators such as sodium persulfate can be used. One skilledin the art will recognize that most initiating systems are applicablehere.

A high degree of chain transfer can lead to crosslinking and formationof an insoluble gel. In one embodiment, this can be avoided by ensuringthat monomer and initiator are fed over the same approximate period oftime. If initiator feed lasts much longer than monomer feed, acrosslinked gel can form, particularly when oligopolysaccharides andpolysaccharides (those having a molecular weight greater than about1000) are used as the chain transfer agent.

As noted above, in some cases the reaction product forms a hybrid gelduring manufacture of these hybrid copolymers. This is especially trueif the synthetic monomer used is extremely reactive (e.g., acrylic acidreacted at low pH (protonated form)) or if the natural chain transferagent has a molecular weight of greater than about 1000. A crosslinkedgel starts to form after the monomer feed has ended and while the restof the initiator is being fed in. This is undesirable in most cases,since the gel product cannot be diluted in water and therefore cannot beused in the applications described below. The exception to this is inthe manufacture of super absorbents, rheology modifiers and gels used totreat wells in the oil field industry.

If an undesirable gel starts to form during the process due to areactive monomer, it can be eliminated in a number of ways. Thisincludes reducing monomer reactivity by neutralizing the monomer,illustrated in Example 10B (neutralizing the monomer duringpolymerization) herein below. As noted in Example 10A, sodium acrylateis far less reactive than acrylic acid and therefore does not form gelsthat acrylic acid may form. In another embodiment, additional chaintransfer agents like thiols, sodium hypophosphite and alcohols can alsobe used. Thiols and alcohols (see, e.g., Example 10C herein below) areparticularly useful in controlling molecular weight and preventing theformation of crosslinked gels. Finally, these gels can be eliminated byshortening the initiator feeds so that the initiator and monomer feedsare pumped over the same period of time (illustrated in Example 10A).

Stabilization of aqueous systems containing scale-forming salts andinorganic particulates involves a variety of mechanisms. Inhibition isone conventional mechanism for eliminating the deleterious effect ofscale-forming salts. In inhibition, synthetic polymer(s) are added thatincrease the solubility of the scale-forming salt in the aqueous system.

Another stabilization mechanism is the dispersion of precipitated saltcrystals. Synthetic polymers having carboxylic acid groups function asgood dispersants for precipitated salts such as calcium carbonates. Inthis mechanism, the crystals stay dispersed rather than dissolving inthe aqueous solution.

A third stabilization mechanism involves interference and distortion ofthe crystal structure of the scale by the polymer, thereby making thescale less adherent to surfaces, other forming crystals and/or existingparticulates.

Hybrid copolymers according to the present invention provide excellentscale inhibition and deposition control under a wide variety ofconditions. For instance, the inventive polymers have been found tominimize calcium carbonate scale formation and deposition by means ofall three mechanisms defined above.

The inventive polymers are further effective at minimizing sulfate scalein oil field treatment applications. The hybrid copolymers are alsohighly effective at dispersing particulate matter such as minerals,clays, salts, metallic ores and metallic oxides. Specific examplesinclude talc, titanium dioxide, mica, silica, silicates, carbon black,iron oxide, kaolin clay, titanium dioxide, calcium carbonate andaluminum oxide. These particulates can be found in a variety ofapplications such as coatings, plastics, rubbers, filtration products,cosmetics, food and paper coatings.

Water Treatment Systems

Water treatment includes prevention of calcium scales due toprecipitation of calcium salts such as calcium carbonate, calciumsulfate and calcium phosphate. These salts are inversely soluble,meaning that their solubility decreases as the temperature increases.For industrial applications where higher temperatures and higherconcentrations of salts are present, this usually translates toprecipitation occurring at the heat transfer surfaces. The precipitatingsalts can then deposit onto the surface, resulting in a layer of calciumscale. The calcium scale can lead to heat transfer loss in the systemand cause overheating of production processes. This scaling can alsopromote localized corrosion.

Calcium phosphate, unlike calcium carbonate, generally is not anaturally occurring problem. However, orthophosphates are commonly addedto industrial systems (and sometimes to municipal water systems) as acorrosion inhibitor for ferrous metals, typically at levels between2.0-20.0 mg/L. Therefore, calcium phosphate precipitation can not onlyresult in those scaling problems previously discussed, but can alsoresult in severe corrosion problems as the orthophosphate is removedfrom solution. As a consequence, industrial cooling systems requireperiodic maintenance wherein the system must be shut down, cleaned andthe water replaced. Lengthening the time between maintenance shutdownssaves costs and is desirable.

It is advantageous to reuse the water in industrial water treatmentsystems as much as possible. Still, water can be lost over time due tovarious mechanisms such as evaporation. As a consequence, dissolved andsuspended solids become more concentrated over time. Cycles ofconcentration refers to the number of times solids in a particularvolume of water are concentrated. The quality of the water makeupdetermines how many cycles of concentration can be tolerated. In coolingtower applications where water makeup is hard (i.e., poor quality), 2 to4 cycles would be considered normal, while 5 and above would representstressed conditions. Hybrid copolymers according to the presentinvention perform particularly well under stressed conditions.

One way to lengthen the time between maintenance in a water treatmentsystem is to use polymers that function in either inhibiting formationof calcium salts or in modifying crystal growth. Crystal growthmodifying polymers alter the crystal morphology from regular structures(e.g., cubic) to irregular structures such as needlelike or florets.Because of the change in form, crystals that are deposited are easilyremoved from the surface simply by mechanical agitation resulting fromwater flowing past the surface. Hybrid copolymers of the presentinvention are particularly useful at inhibiting calcium phosphate basedscale formation such as calcium orthophosphate. Further, these inventivepolymers also modify crystal growth of calcium carbonate scale.

The polymers of the present invention can be added to the aqueoussystems neat, or they can be formulated into various water treatmentcompositions and then added to the aqueous systems. In certain aqueoussystems where large volumes of water are continuously treated tomaintain low levels of deposited matter, the polymers can be used atlevels as low as 0.5 mg/L. The upper limit on the amount of polymer useddepends upon the particular aqueous system treated. For example, whenused to disperse particulate matter the polymer can be used at levelsranging from about 0.5 to about 2,000 mg/L. When used to inhibit theformation or deposition of mineral scale the polymer can be used atlevels ranging from about 0.5 to about 100 mg/L. In another embodimentthe polymer can be used at levels from about 3 to about 20 mg/L, and inanother embodiment from about 5 to about 10 mg/L.

Once prepared, the hybrid copolymers can be incorporated into a watertreatment composition that includes the hybrid copolymer and other watertreatment chemicals. These other chemicals can include, for example,corrosion inhibitors such as orthophosphates, zinc compounds andtolyltriazole. As indicated above, the amount of inventive polymerutilized in the water treatment compositions can vary based upon thetreatment level desired for the particular aqueous system treated. Watertreatment compositions generally contain from about 10 to about 25percent by weight of the hybrid copolymer.

The hybrid copolymers can be used in any aqueous system whereinstabilization of mineral salts is important, such as in heat transferdevices, boilers, secondary oil recovery wells, automatic dishwashers,and substrates that are washed with hard water. The hybrid copolymer isespecially effective under stressed conditions in which other scaleinhibitors fail.

The hybrid copolymers can stabilize many minerals found in water,including, but not limited to, iron, zinc, phosphonate, and manganese.The polymers also disperse particulate found in aqueous systems.

Hybrid copolymers of the present invention can be used to inhibitscales, stabilize minerals and disperse particulates in many types ofprocesses. Examples of such processes include sugar mill anti-sealant;soil conditioning; treatment of water for use in industrial processessuch as mining, oilfields, pulp and paper production, and other similarprocesses; waste water treatment; ground water remediation; waterpurification by processes such as reverse osmosis and desalination;air-washer systems; corrosion inhibition; boiler water treatment; as abiodispersant; and chemical cleaning of scale and corrosion deposits.One skilled in the art can conceive of many other similar applicationsfor which the hybrid copolymer could be useful.

Cleaning Formulations

The polymers of this invention can also be used in a wide variety ofcleaning formulations containing phosphate-based builders. For example,these formulations can be in the form of a powder, liquid or unit dosessuch as tablets or capsules. Further, these formulations can be used toclean a variety of substrates such as clothes, dishes, and hard surfacessuch as bathroom and kitchen surfaces. The formulations can also be usedto clean surfaces in industrial and institutional cleaning applications.

In cleaning formulations, the polymer can be diluted in the wash liquorto the end use level. The polymers are typically dosed at 0.01 to 1000ppm in the aqueous wash solutions. The polymers can minimize depositionof phosphate based scale in fabric, dishwash and hard surface cleaningapplications. The polymers also help in minimizing encrustation onfabrics. Additionally, the polymers minimize filming and spotting ondishes. Dishes can include glass, plastics, china, cutlery, etc. Thepolymers further aid in speeding up the drying processes in thesesystems. While not being bound by theory, it is believed that thehydrophobic nature of these polymers aids in increasing the rate ofdrying on surfaces such as those described above.

Optional components in the detergent formulations include, but are notlimited to, ion exchangers, alkalies, anticorrosion materials,anti-redeposition materials, optical brighteners, fragrances, dyes,fillers, chelating agents, enzymes, fabric whiteners and brighteners,sudsing control agents, solvents, hydrotropes, bleaching agents, bleachprecursors, buffering agents, soil removal agents, soil release agents,fabric softening agent and opacifiers. These optional components maycomprise up to about 90% by weight of the detergent formulation.

The polymers of this invention can be incorporated into hand dish,autodish and hard surface cleaning formulations. The polymers can alsobe incorporated into rinse aid formulations used in autodishformulations. Autodish formulations can contain builders such asphosphates and carbonates, bleaches and bleach activators, andsilicates. These formulations can also include other ingredients such asenzymes, buffers, perfumes, anti-foam agents, processing aids, and soforth. Autodish gel systems containing hypochlorite bleach areparticularly hard on polymers due to the high pH required to maintainbleach stability. In these systems, hydrophobes without an ester group(e.g., aromatics) are particularly useful.

Hard surface cleaning formulations can contain other adjunct ingredientsand carriers. Examples of adjunct ingredients include, withoutlimitation, buffers, builders, chelants, filler salts, dispersants,enzymes, enzyme boosters, perfumes, thickeners, clays, solvents,surfactants and mixtures thereof.

One skilled in the art will recognize that the amount of polymer(s)required depends upon the cleaning formulation and the benefit theyprovide to the formulation. In one aspect, use levels can be about 0.01weight % to about 10 weight % of the cleaning formulation. In anotherembodiment, use levels can be about 0.1 weight % to about 2 weight % ofthe cleaning formulation.

Oilfield Scale Application

Scale formation is a major problem in oilfield applications.Subterranean oil recovery operations can involve the injection of anaqueous solution into the oil formation to help move the oil through theformation and to maintain the pressure in the reservoir as fluids arebeing removed. The injected water, either surface water (lake or river)or seawater (for operations offshore) can contain soluble salts such assulfates and carbonates. These salts tend to be incompatible with ionsalready present in the oil-containing reservoir (formation water). Theformation water can contain high concentrations of certain ions that areencountered at much lower levels in normal surface water, such asstrontium, barium, zinc and calcium. Partially soluble inorganic salts,such as barium sulfate and calcium carbonate, often precipitate from theproduction water as conditions affecting solubility, such as temperatureand pressure, change within the producing well bores and topsides. Thisis especially prevalent when incompatible waters are encountered such asformation water, seawater, or produced water.

Barium sulfate and strontium sulfate form very hard, very insolublescales that are difficult to prevent. Barium sulfate or other inorganicsupersaturated salts can precipitate onto the formation forming scale,thereby clogging the formation and restricting the recovery of oil fromthe reservoir. The insoluble salts can also precipitate onto productiontubing surfaces and associated extraction equipment, limitingproductivity, production efficiency and compromising safety. Certainoil-containing formation waters are known to contain high bariumconcentrations of 400 ppm, and higher. Since barium sulfate forms aparticularly insoluble salt, the solubility of which declines rapidlywith temperature, it is difficult to inhibit scale formation and toprevent plugging of the oil formation and topside processes and safetyequipment.

Dissolution of sulfate scales is difficult, requiring high pH, longcontact times, heat and circulation, and can only be performed topside.Alternatively, milling and in some cases high-pressure water washing canbe used. These are expensive, invasive procedures and require processshutdown. The hybrid copolymers of this invention can minimize sulfatescales, especially downhole sulfate scales.

Dispersant for Particulates

Polymers according to the present invention can be used as a dispersantfor pigments in applications such as paper coatings, paints and othercoating applications. Examples of pigments that can be dispersed by theinventive polymers include titanium dioxide, kaolin clays, modifiedkaolin clays, calcium carbonates and synthetic calcium carbonates, ironoxides, carbon black, talc, mica, silica, silicates, and aluminum oxide.Typically, the more hydrophobic the pigment the better polymersaccording to the present invention perform in dispersing particulates.These particulate matters are found in a variety of applications,including but not limited to, coatings, plastics, rubbers, filtrationproducts, cosmetics, food and paper coatings.

Fiberglass Sizing

Fiberglass is usually sized with phenol-formaldehyde resins orpolyacrylic acid based resins. The former has the disadvantage ofreleasing formaldehyde during end use. The polyacrylic acid resin systemhas become uneconomical due to rising crude oil prices. Hence, there isa need for renewal sizing materials in this industry. The hybridpolymers of this invention are a good fit for this application. They canbe used by themselves or in conjunction with the with the phenolformaldehyde or polyacrylic acid binder system.

The binder composition is generally applied by means of a suitable sprayapplicator to a fiber glass mat as it is being formed. The sprayapplicator aids in distributing the binder solution evenly throughoutthe formed fiberglass mat. Solids are typically present in the aqueoussolution in amounts of about 5 to 25 percent by weight of totalsolution. The binder can also be applied by other means known in theart, including, but not limited to, airless spray, air spray, padding,saturating, and roll coating.

Residual heat from the fibers volatizes water away from the binder. Theresultant high-solids binder-coated fiberglass mat is allowed to expandvertically due to the resiliency of the glass fibers. The fiberglass matis then heated to cure the binder. Typically, curing ovens operate at atemperature of from 130° C. to 325° C. However, the binder compositionof the present invention can be cured at lower temperatures of fromabout 110° C. to about 150° C. In one aspect, the binder composition canbe cured at about 120° C. The fiberglass mat is typically cured fromabout 5 seconds to about 15 minutes. In one aspect the fiberglass mat iscured from about 30 seconds to about 3 minutes. The cure temperature andcure time also depend on both the temperature and level of catalystused. The fiberglass mat can then be compressed for shipping. Animportant property of the fiberglass mat is that it returnssubstantially to its full vertical height once the compression isremoved. The hybrid polymer based binder produces a flexible film thatallows the fiberglass insulation to bounce back after a roll isunwrapped for use in walls/ceilings.

Fiberglass or other non-wovens treated with the copolymer bindercomposition is useful as insulation for heat or sound in the form ofrolls or batts; as a reinforcing mat for roofing and flooring products,ceiling tiles, flooring tiles, as a microglass-based substrate forprinted circuit boards and battery separators; for filter stock and tapestock and for reinforcements in both non-cementatious and cementatiousmasonry coatings.

The following examples are intended to exemplify the present inventionbut are not intended to limit the scope of the invention in any way. Thebreadth and scope of the invention are to be limited solely by theclaims appended hereto.

EXAMPLE 1 Synthesis of Hybrid Copolymer

A reactor containing 200 grams of a 50% solution of citric acid (CA)(0.52 moles) as chain transfer agent was heated to 100° C. A monomersolution containing 238 grams of a 50% solution of sodium2-acrylamido-2-methylpropane sulfonate (NaAMPS) (0.52 moles) was addedto the reactor over a period of 1.5 hours. An initiator solutioncomprising 6.2 grams of sodium persulfate in 100 grams of deionizedwater was simultaneously added to the reactor over a period of 2 hours.The mole percent of citric acid chain transfer agent based on moles ofcitric acid and NaAMPS was 50%. The reaction product was held at 100° C.for an additional 2 hours. The final hybrid copolymer product was agolden yellow solution.

EXAMPLE 2-4 Synthesis of Hybrid Copolymer

Example 1 was repeated but using lower amounts of citric acid as thechain transfer agent. The residual amount of citric acid left insolution was measured by liquid chromatography (“LC”). The amount ofcitric acid incorporated into the polymer was calculated by thedifference of citric acid added to the initial charge and the residualamount measured by GC. The number average molecular weight (Mn) of thesepolymers was measured by gel permeation chromatography (“GPC”).

TABLE I Varying amount of natural constituent during polymerization Mole% CA based Wt % of citric acid on total moles of incorporated intoExample CA + NaAMPS the polymer Mn 1 50 6.4 3536 2 30 4 4867 3 20 1.26481 4 10 0.5 6256The data indicates that the amount of citric acid incorporated into thecopolymer increases as the mole % of CA based on total moles ofCA+NaAMPS increases. Also, the molecular weight of the polymer decreaseswhen increasing amounts of CA are added to the reaction. This loweringof molecular weight clearly demonstrates that citric acid isincorporated into the polymer as a chain transfer agent.

EXAMPLE 5 Synthesis of Hybrid Copolymer

A reactor containing 200 grams of a 50% solution of citric acid (0.52moles) and 212.4 grams of a 50% solution of NaOH (2.65 moles) was heatedto 100° C. A monomer solution containing 100 grams of acrylic acid (1.39moles) was added to the reactor over a period of 1.5 hours. An initiatorsolution comprising of 6.6 grams of sodium persulfate in 30 grams ofdeionized water was simultaneously added to the reactor over a period of2 hours. The reaction product was held at 100° C. for an additionalperiod of 2 hours. The final product was a water white solution.

EXAMPLE 6 Synthesis of Hybrid Copolymer

A reactor containing 25 grams of a 48% solution of gluconic acidsolution and 25 grams of water was heated to 100° C. A monomer solutioncontaining 238 grams of a 50% solution of sodium2-acrylamido-2-methylpropane sulfonate (NaAMPS) (0.52 moles) was addedto the reactor over a period of 1.5 hours. An initiator solutioncomprising of 6.2 grams of sodium persulfate in 100 grams of deionizedwater was simultaneously added to the reactor over a period of 2 hours.The reaction product was held at 100° C. for an additional period of 2hours.

EXAMPLE 7 Synthesis of Hybrid Copolymer

A reactor containing 50 grams of a 48% solution of gluconic acidsolution was heated to 100° C. A monomer solution containing 238 gramsof a 50% solution of sodium 2-acrylamido-2-methylpropane sulfonate(NaAMPS) (0.52 moles) was added to the reactor over a period of 1.5hours. An initiator solution comprising of 6.2 grams of sodiumpersulfate in 100 grams of deionized water was simultaneously added tothe reactor over a period of 2 hours. The reaction product was held at100° C. for an additional period of 2 hours.

EXAMPLE 8 Synthesis of Hybrid Copolymer

A reactor containing 23.8 grams of maltodextrin as a polysaccharidechain transfer agent (Cargill MD™ 01918, spray-dried maltodextrinobtained by enzymatic conversion of common corn starch, available fromCargill Inc., Cedar Rapids, Iowa) dissolved in 119 grams of water washeated to 100° C. A monomer solution containing 238 grams of a 50%solution of sodium 2-acrylamido-2-methylpropane sulfonate (NaAMPS) (0.52moles) was added to the reactor over a period of 1.5 hours. An initiatorsolution comprising of 6.2 grams of sodium persulfate in 100 grams ofdeionized water was simultaneously added to the reactor over a period of2 hours. The reaction product was held at 100° C. for an additional 2hours. The final product was a clear orange solution. The solution wasstable for over a year and did not exhibit any signs of crosslinking.

EXAMPLE 9 Synthesis of Hybrid Copolymer

100 grams of maltodextrin as a polysaccharide chain transfer agent(Cargill MD™ 01918 dextrin, spray-dried maltodextrin obtained byenzymatic conversion of common corn starch, available from Cargill Inc.,Cedar Rapids, Iowa) was initially dissolved in 135 grams of water in areactor heated to 100° C. A monomer solution containing 108 grams ofmethacrylic acid was subsequently added to the reactor over a period of1.5 hours. An initiator solution comprising of 6.2 grams of sodiumpersulfate in 28 grams of deionized water was added to the reactor atthe same time as the monomer solution but over a period of 2 hours. Thereaction product was held at 100° C. for an additional 2 hours. Thepolymer was then neutralized by adding 90.7 grams of a 50% solution ofNaOH.

EXAMPLE 10A Synthesis of Hybrid Copolymer

A reactor containing 50 grams of water was heated to 100° C. A solutioncontaining 50 grams of acrylic acid, 25 grams of maltodextrin (CargillMD™ 01960 dextrin, spray-dried maltodextrin obtained by enzymaticconversion of starch, available from Cargill Inc., Cedar Rapids, Iowa)as a polysaccharide chain transfer agent, and 60 grams of water wasadded to the reactor over a period of 45 minutes. An initiator solutioncomprising of 3.3 grams of sodium persulfate in 28 grams of deionizedwater was simultaneously added to the reactor over the same time frame.(It was noticed that if the initiator feed continued after the monomerfeed, the reaction product became a crosslinked gel, which isundesirable in most cases.) The reaction product was held at 100° C. foran additional 2 hours. The polymer was then neutralized by adding 42.5grams of a 50% solution of NaOH.

The final product was an homogenous amber solution that is stable forseveral months. In contrast, a blend of sodium polyacrylate (ALCOSPERSE®602N polymer, available from Alco Chemical, Chattanooga, Tenn.) andmaltodextrin (Cargill MD™ 01960 dextrin) separated out into phases in aperiod of less than 24 hours. Lack of phase separation in the finalhybrid copolymer illustrates that the acrylic acid polymer is chemicallybonded to the maltodextrin.

EXAMPLE 10B Synthesis of Hybrid Copolymer from Monomer Reduced inReactivity

A reactor containing 75 grams of water and 27.8 grams of 50% NaOH washeated to 100° C. A solution containing 50 grams of acrylic acid, 25grams of maltodextrin (Cargill MD™ 01960 dextrin) as a polysaccharidechain transfer agent, and 60 grams of water was added to the reactorover a period of 45 minutes. An initiator solution comprising of 3.3grams of sodium persulfate in 28 grams of deionized water wassimultaneously added to the reactor over a period of 60 minutes(extending addition of initiator feed beyond addition of the monomerfeed). The reaction product was held at 100° C. for an additional hour.The polymer was a clear amber solution with no signs of crosslinking.This illustrates that crosslinking can be eliminated by reducing thereactivity of the monomer (here, by neutralizing the monomer during thereaction) (contra Example 10A, where the neutralizer was added after thereaction).

EXAMPLE 10C Synthesis of Hybrid Copolymer with Addition of CrosslinkingAgent

A reactor containing 50 grams of water was heated to 100° C. A solutioncontaining 50 grams of acrylic acid, 25 grams of maltodextrin (CargillMD™ 01960 dextrin) as a polysaccharide chain transfer agent, and 60grams of water was added to the reactor over a period of 45 minutes. Aninitiator solution comprising 3.3 grams of sodium persulfate in 28 gramsof deionized water was simultaneously added to the reactor over a periodof 60 minutes hours. After the monomer solution was added, the reactionproduct started to show signs of forming a crosslinked gel. At thispoint, 0.5 grams of isopropanol was added while addition of theinitiator solution was continued. The reaction product returned tosolution almost instantaneously. The reaction product was held at 100°C. for an additional hour. The polymer was then neutralized by adding27.8 grams of a 50% solution of NaOH and 25 grams of water. The finalproduct was a clear dark yellow solution. This illustrates thatcrosslinking noticed in Example 10A can be eliminated by addition of aconventional crosslinking agent such as isopropanol.

EXAMPLE 11 Synthesis of Hybrid Copolymer Using Multiple SyntheticMonomers

A reactor containing 50 grams of water and 50 grams of glycerol as achain transfer agent was heated to 85° C. A solution containing 25 gramsof acrylic acid and 25 grams of styrene was added to the reactor over aperiod of 45 minutes. An initiator solution comprising of 3.3 grams ofsodium persulfate in 30 grams of deionized water was simultaneouslyadded to the reactor over a period of 60 minutes. The reaction productwas held at 85° C. for an additional period of 2 hours. A solution of 28grams of 50% NaOH and 53 grams of water was added to reactor over 60minutes. The final product was an opaque yellow solution.

EXAMPLE 12 Synthesis of Hybrid Copolymer Using Starch as Chain TransferAgent

A reactor containing 50 grams of water was heated to 100° C. A solutioncontaining 50 grams of acrylic acid, 25 grams of a degraded oxidizedstarch (low molecular weight starch with carboxylate groups) as apolysaccharide chain transfer agent, and 60 grams of water was added tothe reactor over a period of 45 minutes. An initiator solutioncomprising of 6.2 grams of sodium persulfate in 28 grams of deionizedwater was simultaneously added to the reactor over a period of 45minutes hours. (It was noticed that if the initiator feed continuedafter the monomer feed, the reaction product became a crosslinked gel,which is unusable.) The reaction product was held at 100° C. for anadditional period of 2 hours. The polymer was then neutralized by adding42.5 grams of a 50% solution of NaOH.

EXAMPLE 13 Synthesis of Super Absorbents and Rheology Modifiers

A reactor containing 50 grams of water was heated to 100° C. A solutioncontaining 50 grams of acrylic acid, 25 grams of maltodextrin (CargillMD™ 01960) as a polysaccharide chain transfer agent, and 60 grams ofwater was added to the reactor over a period of 45 minutes. An initiatorsolution comprising of 3.3 grams of sodium persulfate in 28 grams ofdeionized water was simultaneously added to the reactor over a period of60 minutes hours. A crosslinked gel is formed, which is undesirable inmost cases. However, this type of material can be neutralized and spraydried. The spray dried product can be used as a super absorbent orrheology modifier.

EXAMPLE 14 Dispersancy Evaluation

The polymers of Example 1 and 4 were evaluated in a claysuspension/dispersancy test. A control without any polymer was alsotested. These materials were compared against a sodium polyacrylatesample (NaPAA) (ALCOSPERSE® 602N, available from Alco Chemical,Chattanooga, Tenn.). The samples were prepared by adding 2% clay (50:50rose clay:bandy black clay) to deionized water. The samples were thenstirred on a magnetic stir plate for 20 minutes, after which 0.1% activepolymer was added and the samples were stirred for one minute more. Thesuspensions were then poured into 100 ml graduated cylinders and allowedto rest. FIG. 1 is a photograph of all polymers after a time period ofone hour.

FIG. 1 indicates that the polymers of this invention are excellentdispersants. Furthermore, they are comparable in performance tosynthetic polymers (NaPAA) typically used in this type of application.

EXAMPLE 15 Anti-Redeposition

The polymers of this invention were tested for anti-redepositionproperties in a generic powdered detergent formulation. The powdereddetergent formulation was as follows:

Ingredient wt % Neodol 25-7 10 Sodium carbonate 46 Sodium silicate 3Sodium sulfate 40

The test was conducted in a full scale washing machine using 3 cottonand 3 polyester/cotton swatches. The soil used was 17.5 g rose clay,17.5 g bandy black clay and 6.9 g oil blend (75:25 vegetable/mineral).The test was conducted for 3 cycles using 100 g powder detergent perwash load. The polymers were dosed in at 1.0 weight % of the detergent.The wash conditions used a temperature of 33.9° C. (93° F.), 150 ppmhardness and a 10 minute wash cycle.

L (luminance) a (color component) b (color component) values before thefirst cycle and after the third cycle was measured as L₁, a₁, b₁ and L₂,a₂, b₂, respectively, using a spectrophotometer. ΔE (color difference)values were then calculated using the equation below—

ΔE=[(L ₁ −L ₂)²+(a ₁ −a ₂)²+(b ₁ −b ₂)²]^(0.5)

The data indicate that the polymers of this invention showanti-redeposition/soil suspension properties even at low concentrationsin the wash liquor (a lower ΔE indicates better anti-redepositionproperties).

TABLE 2 Effect on anti-redeposition/soil suspension Delta Whiteness ΔEIndex Sample Cotton Poly/cotton Cotton Poly/cotton Control (no polymer)1.87 1.59 6.67 5.86 Example 3 1.29 0.82 4.48 3.06 Example 8 1.35 0.984.88 3.63

EXAMPLE 16 Hard Surface Cleaning Formulations Acid Cleaner

Ingredient wt % Citric acid (50% solution) 12.0 Phosphoric acid 1.0C₁₂-C₁₅ linear alcohol ethoxylate with 3 moles of EO 5.0 Alkyl benzenesulfonic acid 3.0 Polymer of Example 4 1.0 Water 78.0

Alkaline Cleaner

Ingredient wt % Water 89.0 Sodium tripolyphosphate 2.0 Sodium silicate1.9 NaOH (50%) 0.1 Dipropylene glycol monomethyl ether 5.0 Octylpolyethoxyethanol, 12-13 moles EO 1.0 Polymer of Example 5 1.0

EXAMPLE 17 Automatic Dishwash Powder Formulation

Ingredients wt % Sodium tripolyphosphate 25.0 Sodium carbonate 25.0C12-15 linear alcohol ethoxylate with 7 moles of EO 3.0 Polymer ofExample 10A 4.0 Sodium sulfate 43.0

EXAMPLE 18 Water Treatment Compositions

Once prepared, the water-soluble polymers are preferably incorporatedinto a water treatment composition comprising the water-soluble polymerand other water treatment chemicals. Such other chemicals includecorrosion inhibitors such as orthophosphates, zinc compounds and tolyltriazole. As indicated above, the level of the inventive polymerutilized in the water treatment compositions is determined by thetreatment level desired for the particular aqueous system treated. Thewater treatment compositions generally comprise from 10 to 25 percent byweight of the water-soluble polymer. Conventional water treatmentcompositions are known to those skilled in the art and exemplary watertreatment compositions are set forth in the four formulations below.These compositions containing the polymer of the present invention haveapplication in, for example, the oil field.

Formulation 1 Formulation 2 11.3% of Polymer of Ex. 9 11.3% Polymer ofEx. 6 47.7% Water 59.6% Water  4.2% HEDP  4.2% HEDP 10.3% NaOH 18.4%TKPP 24.5% Sodium Molybdate  7.2% NaOH  2.0% Tolyl triazole  2.0% Tolyltriazole pH 13.0 pH 12.64 Formulation 3 Formulation 4 22.6% of Polymerof Ex. 12 11.3% Polymer of Ex. 1 51.1% Water 59.0% Water  8.3% HEDP 4.2% HEDP 14.0% NaOH 19.3% NaOH  4.0% Tolyl triazole  2.0% Tolyltriazole pH 12.5  4.2% ZnCl₂ pH 13.2where HEDP is 1-hydroxyethylidene-1,1 diphosphonic acid and TKPP istri-potassium polyphosphate.

EXAMPLE 19 Cement Composition

Various quantities of the polymer produced as described in Example 1above (9% by weight aqueous solution of the polymer) were added to testportions of a base cement slurry. The base cement composition includedLone Star Class H hydraulic cement and water in an amount of 38% byweight of dry cement. The base composition had a density of 16.4 poundsper gallon. These compositions containing the polymer of the presentinvention have application in, for example, the oil field.

EXAMPLE 20 Automatic Non-Phosphate Dishwash Powder Formulation

Ingredients wt % Sodium citrate 30 Polymer of Example 1 10 Sodiumdisilicate 10 Perborate monohydrate 6 Tetraacetylethylenediamine 2Enzymes 2 Sodium sulfate 30

EXAMPLE 21 Handwash Fabric Detergent

Ingredients wt % Linear alkylbenzene sulfonate 15-30  Nonionicsurfactant 0-3  Na tripolyphosphate (STPP) 3-20 Na silicate 5-10 Nasulfate 20-50  Bentonite clay/calcite 0-15 Polymer of Example 4 1-10Water Balance

EXAMPLE 22 Fabric Detergent with Softener

Ingredients wt % Linear alkylbenzene sulfonate 2 Alcohol ethoxylate 4STPP 23 Polymer of Example 11 1 Na carbonate 5 Perborate tetrahydrate 12Montmorillonite clay 16 Na sulfate 20 Perfume, FWA, enzymes, waterBalance

EXAMPLE 23 Bar/Paste for Laundering

Ingredients wt % Linear alkylbenzene sulfonate 15-30  Na silicate 2-5 STPP 2-10 Polymer of Example 10A 2-10 Na carbonate 5-10 Calcite 0-20Urea 0-2  Glycerol 0-2  Kaolin 0-15 Na sulfate 5-20 Perfume, FWA,enzymes, water Balance

EXAMPLE 24 Liquid Detergent Formulation

Ingredients wt % Linear alkyl benzene sulfonate 10 Alkyl sulfate 4Alcohol (C₁₂-C₁₅) ethoxylate 12 Fatty acid 10 Oleic acid 4 Citric acid 1NaOH 3.4 Propanediol 1.5 Ethanol 5 Polymer of Example 11 1 Ethanoloxidase 5 u/ml Water, perfume, minors up to 100

Although the present invention has been described and illustrated indetail, it is to be understood that the same is by way of illustrationand example only, and is not to be taken as a limitation. The spirit andscope of the present invention are to be limited only by the terms ofany claims presented hereafter.

1.-17. (canceled)
 18. A hybrid copolymer comprising: a synthetic polymercomprising at least one hydrophilic acid monomeric unit wherein the atleast one hydrophilic acid monomeric unit is acrylic acid ormethacrylate acid or salts thereof or mixtures thereof; and a naturallyderived hydroxyl containing chain transfer agent as the end group,wherein the naturally derived hydroxyl containing chain transfer agentis a monosaccharide, disaccharide, oligosaccharide or polysaccharide.19. The copolymer of claim 18 wherein the at least one hydrophilic acidmonomeric unit further comprises maleic acid, itaconic acid or saltsthereof or mixtures thereof.
 20. The copolymer of claim 18 wherein theat least one hydrophilic acid monomeric unit further comprises2-acrylamido-2-methyl propane sulfonic acid or a salt thereof.
 21. Thecopolymer of claim 18 wherein the synthetic polymer comprises ahydrophobic monomeric unit and a hydrophilic acid monomeric unit. 22.The copolymer of claim 21 wherein the hydrophobic monomeric unit ischosen from the group consisting of styrene, a-methyl styrene, methylmethacrylate, methyl acrylate, 2-ethylhexyl acrylate, octyl acrylate,lauryl acrylate, stearyl acrylate, 2-ethylhexyl methacrylate, octylmethacrylate, lauryl methacrylate, stearyl methacrylate, behenylmethacrylate and octyl acrylamide.
 23. The copolymer of claim 18 whereinthe polysaccharide is chosen from the group consisting of starch,cellulose, pectin, alginate, gellan, gums and modified starch.
 24. Thecopolymer of claim 23 wherein the starch is chosen from the groupconsisting of maize, potato, tapioca, wheat, rice, pea, sago, oat,barley, rye and amaranth.
 25. The copolymer of claim 24 wherein thestarch is chosen from the group consisting of waxy starch, high amylosestarch, maltodextrins and oxidized starch.
 26. A formulation comprising:(a) a hybrid copolymer comprising: (i) a synthetic polymer comprising atleast one hydrophilic acid monomeric unit wherein the at least onehydrophilic acid monomeric unit is acrylic acid or a salt thereof, and(ii) a naturally derived hydroxyl containing chain transfer agent as theend group, wherein the naturally derived hydroxyl containing chaintransfer agent is a monosaccharide, disaccharide, oligosaccharide orpolysaccharide; and (b) at least one adjunct ingredient.
 27. Theformulation of claim 26 wherein the formulation is selected from thegroup consisting of a cleaning, superabsorbent, fiberglass binder,rheology modifier, oil field, water treatment, dispersant and a cementformulation.
 28. The formulation of claim 27 wherein the cleaningformulation is a detergent, fabric cleaner, automatic dishwashingdetergent, glass cleaner, hard surface cleaner or a laundry detergent.29. The formulation of claim 28 wherein the automatic dishwashingdetergent is a non-phosphate formulation.
 30. The formulation of claim26 wherein the adjunct ingredient is selected from the group consistingof water, surfactants, builders, phosphates, sodium carbonate, citrates,enzymes, buffers, perfumes, anti-foam agents, ion exchangers, alkalis,anti-redeposition materials, optical brighteners, fragrances, dyes,fillers, chelating agents, fabric whiteners, brighteners, sudsingcontrol agents, solvents, hydrotropes, bleaching agents, bleachprecursors, buffering agents, soil removal agents, soil release agents,fabric softening agent, opacifiers, water treatment chemicals, corrosioninhibitors, orthophosphates, zinc compounds, tolyltriazole, minerals,clays, salts, metallic ores, metallic oxides, talc, pigments, titaniumdioxide, mica, silica, silicates, carbon black, iron oxide, kaolin clay,modified kaolin clays, calcium carbonate, phosphonates, syntheticcalcium carbonates, fiberglass, cement and aluminum oxide.
 31. Themethod of cleaning of claim 30 wherein the adjunct ingredient isselected from the group consisting of water, surfactants, builders,phosphates, sodium carbonate, citrates, enzymes, buffers, perfumes,anti-foam agents, ion exchangers, alkalies, anticorrosion materials,anti-redeposition materials, optical brighteners, fragrances, dyes,fillers, chelating agents, fabric whiteners, brighteners, sudsingcontrol agents, solvents, hydrotropes, bleaching agents, bleachprecursors, buffering agents, soil removal agents, soil release agents,phosphonates, fabric softening agents and opacifiers.
 32. The method ofcontrolling scale of claim 31 wherein the scale controlled is carbonate,sulfate, phosphate or silicate based scales.
 33. A method for dispersingparticulates in an aqueous system, the method comprising adding to theaqueous system the hybrid copolymer according to claim 18 in an amountsufficient to disperse the particulates.
 34. The method of dispersingparticulates of claim 33 wherein the particulates are minerals, clays,salts, metallic ores, metallic oxides, dirt, soils, talc, pigments,titanium dioxide, mica, silica, silicates, carbon black, iron oxide,kaolin clay, calcium carbonate, synthetic calcium carbonates,precipitated calcium carbonate, ground calcium carbonate, precipitatedsilica, kaolin clay or combinations thereof.
 35. The copolymer of claim18 wherein the synthetic polymer is present at between 25 and 99.9percent by weight of the copolymer.
 36. A hybrid copolymer formed bycombining at least one hydrophilic acid monomer with a solution of anaturally derived hydroxyl containing chain transfer agent and aninitiator that is not a metal based redox system at a temperatureeffective to activate the initiator, wherein the at least onehydrophilic acid monomer is acrylic acid, methacrylic acid or saltsthereof or mixtures thereof, and wherein the naturally derived hydroxylcontaining chain transfer agent is a monosaccharide, disaccharide,oligosaccharide or polysaccharide.
 37. The hybrid copolymer of claim 36wherein the initiator is persulfate.
 38. The hybrid copolymer of claim36 wherein the at least one hydrophilic acid monome further comprisesmaleic acid, itaconic acid or salts thereof or mixtures thereof.
 39. Thehybrid copolymer of claim 36 wherein the at least one hydrophilic acidmonomer further comprises 2-acrylamido-2-methyl propane sulfonic acid ora salt thereof.